US6912874B2 - Device and process for introducing gases into a hot medium - Google Patents

Device and process for introducing gases into a hot medium Download PDF

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Publication number
US6912874B2
US6912874B2 US09/943,739 US94373901A US6912874B2 US 6912874 B2 US6912874 B2 US 6912874B2 US 94373901 A US94373901 A US 94373901A US 6912874 B2 US6912874 B2 US 6912874B2
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United States
Prior art keywords
gas
pipe
platinum
glass
hot medium
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US09/943,739
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US20020069673A1 (en
Inventor
Christian Kunert
Werner Kiefer
Hildegard Roemer
Uwe Kolberg
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Schott AG
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Schott Glaswerke AG
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Assigned to GLAS, SCHOTT reassignment GLAS, SCHOTT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIEFER, WERNER, KOLBERG, UWE, KUNERT, CHRISTIAN, ROEMER, HILDEGARD
Publication of US20020069673A1 publication Critical patent/US20020069673A1/en
Assigned to SCHOTT AG reassignment SCHOTT AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHOTT GLAS
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Publication of US6912874B2 publication Critical patent/US6912874B2/en
Assigned to SCHOTT GLAS reassignment SCHOTT GLAS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FINNERTY, PAUL JOSEPH, THORNE, ALFRED JAMES
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/231—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids by bubbling
    • B01F23/23105—Arrangement or manipulation of the gas bubbling devices
    • B01F23/2312—Diffusers
    • B01F23/23121—Diffusers having injection means, e.g. nozzles with circumferential outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F35/93—Heating or cooling systems arranged inside the receptacle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/005—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out at high temperatures in the presence of a molten material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/193—Stirring devices; Homogenisation using gas, e.g. bubblers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F2035/98—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00119—Heat exchange inside a feeding nozzle or nozzle reactor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/6416—With heating or cooling of the system
    • Y10T137/6579—Circulating fluid in heat exchange relationship
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/6851—With casing, support, protector or static constructional installations
    • Y10T137/7036—Jacketed

Definitions

  • a replacement of the platinum feed pipe that is dipped from above into the melt by pipes of other materials, such as ceramic or silica glass, does not result in a permanent solution of the problem, since all materials dissolve in a few hours in the aggressive melts and thus are not suitable for continuous glass production.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

This invention relates to a device and a process for introducing gases into a hot medium, whereby device (1) contains a pipe (2) for introducing gas and a cooling jacket (3) that encases pipe (2).

Description

This invention relates to a device and a process for introducing gases into a hot medium.
In the continuous production of laser glass for high-performance lasers, the glass raw materials are melted in a melting basin. When leaving the melting basin, the water content is considerably above what is needed for use as laser glass. The glass is therefore fed into a purification and drying stage, in which a mixture that consists of oxygen and chlorine gas is introduced into the melt in different proportions. The temperatures in the melt are approximately 1400° C. Then, the glass is set for shaping with respect to homogeneity and temperature and brought into the desired shape.
To achieve the required low absorption in a light wave length above 2.7 μm, a very low water content, and therefore a very low content of hydroxyl groups, must be ensured. The required low water content can be achieved in the case of intermittent melting by a long holding time of the melt and introduction of oxygen.
In the case of a continuous aggregate, long holding times and processing times cannot be performed economically. As a very efficient desiccant, chlorine gas is introduced into the melt. Since platinum metal is usually resistant to the glass melt at the temperatures that occur, a platinum pipe is used for introducing chlorine gas. The latter is dipped from above into the crucible to a point just above the bottom. Chlorine gas is introduced via the platinum pipe. The chlorine gas bubbles through the melt from below. In this case, the drying action is carried out. Since the platinum pipe is located in the hot melt, it also reaches temperatures of above 1000° C. It has been shown that at these temperatures, a platinum pipe is perforated and partially dissolved by the aggressive chlorine gas within a short operating time. The function of the gas introduction is then not ensured, so that the water content increases to unacceptably high values. In addition, via the dissolved platinum, it results in an unacceptably high number of platinum pockets in the glass. As a result, the production must be halted after just a short time.
In the production of glasses that must meet high quality requirements, it is a common process to introduce gases into the glass melts to cause reactions determined by the gases that are introduced. By the introduction of oxygen or reducing gases, coloring polyvalent ions that are contained in the glass can be adjusted in a specific fashion in their oxidation stage to achieve a desired color of the glass or else to prevent an undesirable discoloration of the glass. In small melt aggregates, in this respect, usually suitably bent pipes that consist of materials that withstand the melting temperatures and that do not contaminate the melts, such as silica glass or platinum, are introduced into the melt from above to a point just above the bottom of the crucible.
In industrial aggregates, gases are also introduced into the melts at various points. For the most part, the so-called bubbling nozzles are used in a specific influencing of the flow into the glass-melting tanks. In such cases, generally oxygen, rare air or inert gases are used. Reactive gases can also exert influence on chemical reactions in the glass melt.
The standard processes for introducing gas into melts are not applicable in the continuous production of aggressive glass melts, especially phosphate glass melts for high-performance lasers. Platinum pipes that are dipped from above into the melts are partially dissolved and perforated in a short time, so that the pipe can no longer perform its function. In addition, the strong dissolution of the platinum results in the formation of a considerable number of extremely small platinum particles in the glass melt, by which glass that is produced from the melt is of no use as laser glass.
A replacement of the platinum feed pipe that is dipped from above into the melt by pipes of other materials, such as ceramic or silica glass, does not result in a permanent solution of the problem, since all materials dissolve in a few hours in the aggressive melts and thus are not suitable for continuous glass production.
An introduction of the gas through the bottom of the vessel that contains the melt was previously not possible because of the corrosive action of the aggressive melts, which destroyed all known materials. The corrosion and destruction of the gas feed device at the bottom of the melting vessel resulted in a draining-out of the entire melt and thus a considerable threat to personnel as well as a longer-term interruption of production.
The object of this invention is to provide a device and an economical and nonpolluting process, whereby gases are introduced into a hot medium over a longer period without damage or dissolution of the device by the gas occurring.
The object of the invention is achieved by a device for introducing gases in a hot medium, whereby the device contains a pipe for introducing gas and a cooling jacket that encases the pipe.
An aggressive gas is fed through the device according to the invention, whereby the contact surfaces of the device to the gas are kept below a critical temperature, above which the material of the device would react with the aggressive gas, by a suitable cooling.
In the device according to the invention, the parts that have contact with gases, such as chlorine gas, are adequately cooled. Thus, the pipe that is made of metal, such as platinum, is not hot while it is in contact with chlorine gas. By suitable cooling, the device according to the invention ensures that all metal surfaces that are not covered by glass and that can come into contact with the gases do not heat up above a critical temperature, in which the metals that are used are dissolved by the gases that are used. The cooling jacket encases the pipe, preferably up to its orifice.
According to a preferred embodiment of the invention, the cooled contact surfaces are coated with a layer that is chemically resistant to chlorine gas at the prevailing temperatures. The layer can consist of a thin platinum layer which is applied to another structural material. Plastics with a high fluorine content can also be used, however. By the cooling, it is ensured that the decomposition temperature of the plastic is not exceeded. In this embodiment, a considerable number of materials, such as steel, can be used as construction materials. As a result, the amount of noble metal that is used is considerably reduced, by which the device is significantly more economical both in production and in use.
In the device according to the invention, gas or a gas mixture, oil or an oil mixture, silicone oil or a silicone oil mixture, especially water or an aqueous solution, are used as coolants for the cooling jacket. This coolant is economical and nonpolluting.
The material of the contact surfaces of the device according to the invention preferably consists of platinum or a platinum alloy. The contact surfaces, uncoated, come into contact with the chlorine gas. Especially good results are achieved with this material.
The aggressive gas, such as chlorine, is introduced preferably into a glass-melting tank, a lower part thereof or a crucible by means of the device according to the invention. In addition, for example, chlorine is introduced into refining parts and conditioning parts by means of the device according to the invention.
The process according to the invention is preferably performed continuously. In the continuous production of laser glass, an introduction of chlorine gas from below is impossible to date, since a leak at the bottom of the crucible caused all of the glass that was contained to drain out. This problem was remedied with the invention according to the invention.
The invention makes available a device with which aggressive gases, such as chlorine gas, are reliably introduced over an extended period into hot glass melts, without damage or dissolution of the device by the aggressive gas occurring. Besides pure or technical chlorine gas, gases containing chlorine, like SiCl4 or CCl4, or mixtures of chlorine gas, chlorine containing gases or other gases could be used as well.
The invention is explained in more detail based on a drawing.
DRAWINGS
The drawing consists of FIGS. 1 to 3.
FIG. 1 shows: a device (1) according to the invention, whereby the reaction gas is fed through pipe (2). The coolant is introduced (4) into cooling jacket (3) and removed therefrom (5). Cooling jacket (3) encases pipe (2), preferably up to its orifice (2 a).
FIG. 2 shows: device (1) according to the invention whereby the gas is introduced into melt (6) in the purification and drying stage from below. For melt (6), glass is sent to be melted (7) and drained off (8) for further processing. To this end, device (1) is fitted gastight into a recess (9) in bottom (10) of the purification and drying stage and sealed shut if necessary.
FIG. 3 shows: the purification and drying stage as in FIG. 2 with the difference that in device (1) according to the invention, the gas is introduced into melt (6) from above. To this end, device (1) dips from above into melt (6) to a point just above the bottom of crucible (11).
The variant embodiment according to FIG. 3 is preferably used where an existing unit must be added later to a gas feed device. Since the cooled surfaces that have contact with the glass melts are significantly larger than in FIG. 2, in this case the removal of heat from the melt is also greater. This must be compensated by a correspondingly stronger heating of the melt.
The entire disclosure of all applications, patents and publications, cited above and below, and of corresponding German Application No. 100 43 872.5, filed Sep. 4, 2000 is hereby incorporated by reference.

Claims (20)

1. A device for introducing a gas into a hot medium, comprising a pipe having an orifice and a cooling jacket that encases said pipe to its orifice, wherein the surface of the pipe and/or cooling jacket that is in contact with the gas that is to be introduced is platinum or a platinum alloy.
2. A device according to claim 1, wherein a coolant is present in the cooling jacket wherein said coolant is a gas or a gas mixture, an oil or an oil mixture, a silicone oil or a silicone oil mixture, water or an aqueous solution.
3. A combination of a device according to claim 1 and a hot medium, wherein the hot medium is melted glass.
4. A combination of a device according to claim 1 and a glass-melting tank or a crucible, wherein a hot medium is in the glass-melting tank or in the crucible.
5. A combination according to claim 4, wherein the device reaches into the hot medium from the surface of the hot medium.
6. A combination according to claim 5, wherein the hot medium is melted glass.
7. A device according to claim 1, wherein the pipe is made of steel and has a platinum or platinum alloy layer on the surface that is to be in contact with the gas that is to be introduced.
8. A device according to claim 1, wherein the pipe is made of a material other than platinum or a platinum alloy and has a platinum or platinum alloy layer on the surface that is to be in contact with the gas that is to be introduced.
9. A device for introducing a gas into a hot medium, comprising a pipe and a cooling jacket that encases said pipe, wherein the pipe is made of a plastic with fluorine content and has a platinum or platinum alloy layer on the surface that is to be in contact with the gas that is to be introduced.
10. A combination of
(1) a device for introducing a gas into a hot medium, said device comprising a pipe and a cooling jacket that encases said pipe, wherein the surface of the pipe and/or cooling jacket that is in contact with the gas that is to be introduced is platinum or a platinum alloy and
(2) a gas that is introduced, wherein the gas that is introduced is chlorine gas or a mixture of gases containing chlorine gas.
11. A process for introducing a gas into a hot medium, comprising passing the gas into the hot medium via a device according to claim 1.
12. A process according to claim 11, wherein the cooling jacket is cooled with water or an aqueous solution.
13. A process according to claim 11, wherein the gas is chlorine gas or a mixture of gases containing chlorine gas.
14. A process according to claim 11, wherein the hot medium is melted glass.
15. A process according to claim 11, wherein the gas is introduced into a glass-melting tank or into a crucible.
16. A process according to claim 11, wherein the process is performed continuously.
17. A method for preparing a laser glass comprising introducing a gas into a glass melt from which the laser glass is to be produced through a device which is in accord to claim 1.
18. A method according to claim 17, wherein the method is performed continuously.
19. A method according to claim 17, wherein the gas is chlorine gas or a mixture of gases containing chlorine gas.
20. A method according to claim 17, wherein the pipe is made of steel and has a platinum or platinum alloy layer on the surface that is to be in contact with the gas that is to be introduced.
US09/943,739 2000-09-04 2001-09-04 Device and process for introducing gases into a hot medium Expired - Lifetime US6912874B2 (en)

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DE10043872 2000-09-04
DE10043872.5 2000-09-04

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US6912874B2 true US6912874B2 (en) 2005-07-05

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JP (1) JP5075311B2 (en)
DE (1) DE10142405B4 (en)
FR (1) FR2813536B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100242543A1 (en) * 2006-08-12 2010-09-30 Simone Monika Ritter Method and system for producing glass, in which chemical reduction of glass components is avoided
US10570045B2 (en) 2015-05-22 2020-02-25 John Hart Miller Glass and other material melting systems

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10144474B4 (en) * 2001-09-10 2005-04-14 Schott Ag Process for the preparation of bismuth oxide-containing glasses and use of the process for producing optical glasses
US7854144B2 (en) * 2005-07-28 2010-12-21 Corning Incorporated Method of reducing gaseous inclusions in a glass making process
US7584632B2 (en) * 2005-07-28 2009-09-08 Corning Incorporated Method of increasing the effectiveness of a fining agent in a glass melt
US20090320525A1 (en) * 2008-06-26 2009-12-31 William Weston Johnson Method of bubbling a gas into a glass melt
US20100199721A1 (en) * 2008-11-12 2010-08-12 Keisha Chantelle Ann Antoine Apparatus and method for reducing gaseous inclusions in a glass

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US2155315A (en) * 1938-03-07 1939-04-18 Harshaw Chem Corp Apparatus for making aqueous hydrofluoric acid
GB658141A (en) 1948-12-02 1951-10-03 Wiener Radiowerke Ag Improvements in the manufacture of articles of refined glass
US3397973A (en) 1958-10-23 1968-08-20 Owens Illinois Inc Bubbler apparatus for a glass melting furnace
US4550898A (en) 1984-06-04 1985-11-05 Labate Ii Michael D Air cooled refractory lance
US4600425A (en) * 1985-03-29 1986-07-15 Ppg Industries, Inc. Bubbler with protective sleeve or fluid coolant jacket
JPH0280328A (en) * 1988-09-16 1990-03-20 Shiro Takahashi Treatment of molten glass
JPH0294364A (en) * 1988-09-20 1990-04-05 Reiko Notoya Electrode for oxygen electrode reaction and manufacture thereof
DE4136552A1 (en) 1991-11-06 1993-05-13 Kortec Ag NOZZLE DEVICE FOR INITIATING MEDIA INTO A MELT AND METHOD FOR OPERATING THIS NOZZLE DEVICE
DE19947729A1 (en) 1998-10-08 2000-04-27 Carbon Ind Produkte Gmbh Gas introduction system for melt baths

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US2155315A (en) * 1938-03-07 1939-04-18 Harshaw Chem Corp Apparatus for making aqueous hydrofluoric acid
GB658141A (en) 1948-12-02 1951-10-03 Wiener Radiowerke Ag Improvements in the manufacture of articles of refined glass
US3397973A (en) 1958-10-23 1968-08-20 Owens Illinois Inc Bubbler apparatus for a glass melting furnace
US4550898A (en) 1984-06-04 1985-11-05 Labate Ii Michael D Air cooled refractory lance
US4600425A (en) * 1985-03-29 1986-07-15 Ppg Industries, Inc. Bubbler with protective sleeve or fluid coolant jacket
JPH0280328A (en) * 1988-09-16 1990-03-20 Shiro Takahashi Treatment of molten glass
JPH0294364A (en) * 1988-09-20 1990-04-05 Reiko Notoya Electrode for oxygen electrode reaction and manufacture thereof
DE4136552A1 (en) 1991-11-06 1993-05-13 Kortec Ag NOZZLE DEVICE FOR INITIATING MEDIA INTO A MELT AND METHOD FOR OPERATING THIS NOZZLE DEVICE
DE19947729A1 (en) 1998-10-08 2000-04-27 Carbon Ind Produkte Gmbh Gas introduction system for melt baths

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100242543A1 (en) * 2006-08-12 2010-09-30 Simone Monika Ritter Method and system for producing glass, in which chemical reduction of glass components is avoided
US8347655B2 (en) * 2006-08-12 2013-01-08 Schott Ag Method and system for producing glass, in which chemical reduction of glass components is avoided
US10570045B2 (en) 2015-05-22 2020-02-25 John Hart Miller Glass and other material melting systems

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Publication number Publication date
JP2002145625A (en) 2002-05-22
JP5075311B2 (en) 2012-11-21
DE10142405A1 (en) 2002-03-28
FR2813536A1 (en) 2002-03-08
US20020069673A1 (en) 2002-06-13
FR2813536B1 (en) 2004-08-27
DE10142405B4 (en) 2011-09-15

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